NJC
23.4, 117.3, 110.6, 29.1, 26.7, 23.6, 23.3. C21
Paper
1
H
24
N
2
O, P2
1
/c, 123.7, 120.0, 116.8, 111.4, 110.9. C20
H N O
14 2 2
, P1%, a = 9.9809(7),
a = 8.47970(10), b = 15.0831(2), c = 28.0078(4) Å, b = 93.3600(10)1, b = 10.7407(4), c = 14.9870(10) Å, a = 73.451(5)1, b = 78.454(6)1,
3
3
V = 3576.04 Å , Z = 8, R = 0.038, CCDC #1538860.†
g = 86.790(4)1, V = 1508.92 Å , Z = 4, R = 0.044, CCDC 1538865.†
1
1
Complexes
1
-Methyl-3(phenylimino)-5-bromo-indolinone-2-one (L5). IR
[
Cu(L1) ](Cl) (C1). A methanol solution containing 500 mg
2 2
ꢀ1
(
KBr) n, cm : 1729 (nCQO), 1653 (nCQN). MS (ESI), m/z (%):
39.12.09, 254.09. H NMR (CD
.64, 7.53–7.48, 7.37–7.30, 7.17, 7.01–6.96, 6.95–6.89 (m, 6.69H),
.5 (d, J = 6.8 Hz), 3.21 (s, 2.19 H), 3.09 (s, 0.56 H). C NMR
(
3 mmol) of CuCl
containing 1.38 mg (6 mmol) of L1. The mixture was mixed for
h and filtered. The formed dark brown complex solution was
left for crystallization at r.t. for several days to form small
prismatic crystals of [Cu(L1) ]Cl . Yield: 90%. MW = 606.99.
Calculated for C H Cl CuN O – C (59,36), H (3,99), N (9,23);
2
ꢁ2H
2
O was mixed with a methanol solution
1
3
7
6
(
1
3
CN), d, ppm: 7.79–7.75, 7.68–
1
1
3
CD CN), d, ppm: 151.5, 148.6, 137.5, 130.8, 129.6, 129.0, 126.5,
3
2
2
20.1, 118.3, 114.9, 112.6, 26.9. C15
b = 16.2246(4), c = 19.1312(4) Å, b = 95.696(2)1, V = 2505.32 Å ,
Z = 8, R = 0.035, CCDC #1538858.†
2
H11BrN O, C2/c, a = 8.1114(2),
3
0
24
2
4 2
3
ꢀ1
estimated – C (59,36), H (3,99), N (9,23). IR (KBr) n, cm : 1728
1
+
(
[
nC=O), 1659 (n
). ESI (MeOH), m/z: 608.06 [M] , 570.088
CQN
+
+
M ꢀCl] , 535.11 [M ꢀ2Cl] . C30
2 4 2
H24Cl CuN O
, P1%, a = 8.0870(8),
1
-Methyl-3(phenylimino)-5-methyl-indolinone-2-one (L6). IR
ꢀ1
b = 9.2417(10), c = 9.6103(10) Å, a = 75.944(9)1, b = 75.005(9)1, g =
(
KBr) n, cm : 1737 (nCQO), 1646 (nCQN). MS (ESI), m/z (%):
71.118, 273.100. H NMR (CD
.06, 6.99–6.93, 6.66–6.63 (m), 6.28 (s, br), 3.19 (s, J = 6.2 Hz,
3
2H), 3.14 (s, 2H), 3.07 (s, 3H), 2.00 (s, 13H). C NMR (CD CN),
d, ppm: 207.5, 163.9, 155.9, 151.9, 147.3, 139.7, 135.5, 132.7,
30.6, 130.1, 129.9, 127.1, 126.0, 125.5, 123.7, 119.9, 118.3, 115.6,
12.1, 110.9, 110.5, 110.0, 89.9, 89.6, 30.9, 26.7, 20.8. C16 H14 N2
O1, P2 /m, a = 9.0075(8), b = 6.8883(8), c = 10.3867(11) Å, b =
8.932(8)1, V = 636.642 Å , Z = 2, R
3
1
7
9.112(9)1, V = 666.903 Å , Z = 1, R
1
= 0.028, CCDC #1538868.†
2
7
1
3
CN), d, ppm: 7.53–7.41, 7.39–
[
Cu (m-Cl) (L7) ] (C2). A methanol solution containing 500 mg
1
3
2
2
2
(
3 mmol) of CuCl
2
ꢁ2H
2
O was mixed with a MeOH solution
containing 820 mg (3 mmol) of L7. To the resulting brown
colored solution, 1.55 mL of 10% iPrSH (3 mmol) methanol
solution was gradually (to prevent copper(I) thiolate formation)
added to the complex C1. The color changed from brown to dark
green. The mixture was stirred for 1 h and filtered. The resulting
solution was allowed to evaporate for 24 h, resulting in dark
green crystalline product formation of binuclear complex
1
1
1
3
9
1
= 0.070, CCDC 1538861.†
1-Methyl-3(2,4,6-trimethyl-phenylimino)-indolinone-2-one (L7).
ꢀ
1
IR (KBr) n, cm : 1729 (nCQO), 1656 (nCQN). MS (ESI), m/z (%):
79.150. H NMR (CD CN), d, ppm: 7.39 (td, J = 7.8, 1.2 Hz, 1H),
.96 (s, 2.5H), 6.94 (s, 0.5H), 6.74 (td, J = 7.6, 8.0 Hz, 1H), 6.31
dd, J = 7.6, 0.6 Hz, 1H), 6.31 (dd, J = 7.6, 0.6 Hz, 1H), 3.22 (s,
H), 2.30 (s, 3H), 1.92 (s, 6H). C NMR (CD CN), d, ppm: 163.6,
3
56.6, 148.9, 147.0, 135.4, 134.8, 130.0, 125.4, 124.9, 123.7,
17.5, 110.5, 26.7, 20.9, 17.8.
18 18 2 2 1
C H N O , P2 /c, a = 6.9194(4), b = 8.6089(5), c =
4.9101(16) Å, b = 96.141(6)1, V = 1475.34 Å , Z = 4, R
.044, CCDC 1538862.†
ꢀ1
1
[
C
1
Cu
2
(m-Cl)
2
(L7)
Cu
4.316(6) Å, b = 114.64(5)1, V = 1643.55 Å , Z = 2, R
CCDC #1538877.†
2
]. MW = 754.59. IR (KBr) n, cm : 1718 (nCQO).
2
6
(
3
1
1
3
36
H36Cl
2
2
N
4
O
2
, P2 /c, a = 15.435(8), b = 8.1831(15) c =
1
3
1
= 0.145,
1
3
[
Cu (m-Br) (L7) ] (C3). Th complex was prepared by two
2 2 2
methods:
A) A MeCN solution containing 500 mg of CuBr (3.5 mmol)
(
3
2
0
=
1
was mixed with acetonitrile solution containing 1 g (3.5 mmol)
of L7, and the resulting solution was stirred for 1 h, filtered
and allowed to slowly evaporate. In 24 h, thin plate crystals
ꢀ
1
1-Isopropyl-3(phenylimino)indolinone-2-one (L8). IR (KBr) n, cm
:
1
724 (nCQO), 1662 (nCQN). MS (ESI), m/z (%): 265.134, 287.116. of [Cu
2
(m-Br)
2
(L7)
2
] were formed on the walls of the beaker.
Cu – C (51,25),
.42 (m, 1.72H), 7.39–7.30 (m, 1.13H), 7.30–7.22 (m, 0.77H), H (4,30), N (6,64); estimated – C (50,67), H (3,36), N (6,71). IR (KBr)
1
H NMR (CD CN), d, ppm: 7.64 (dd, J = 7.4, 0.6 Hz, 0.18H), 7.52– MW = 843.60. Calculated for C36
H
36Br
N O
2 4 2
3
2
7
7
0
7
1
1
1
ꢀ
1
.18–7.06 (m, 1.37H), 6.99–6.91 (m, 1.87H), 6.70 (td, J = 7.7, n, cm : 1717 (nCQO). C36
.8 Hz, 0.8H), 6.48 (dd, J = 7.7, 0.9 Hz, 0.8H), 4.57 (hept, J = b = 7.92427(19), c = 14.7380(5) Å, b = 112.819(4)1, V = 1659.98 Å ,
.0 Hz, 0.8H), 4.49–4.37 (m, 0.2H), 1.50 (d, J = 7.0 Hz, 4.75H), Z = 2, R = 0.033, CCDC #1538873.†
(B) To a methanol solution containing 500 mg (2.2 mmol)
63.4, 155.8, 152.0, 148.3, 134.9, 130.6, 129.4, 126.8, 125.9, of CuBr , L7 dissolved in MeOH was gradually added under
23.5, 122.7, 119.7, 118.1, 117.1, 111.9, 111.5, 45.3, 45.0, 19.5. slight heating. Reaction resulted in the formation of dark-green
2 2 4 2 1
H36Br Cu N O , P2 /c, a = 15.4205(6),
3
1
1
3
3
.42 (d, J = 7.0 Hz, 1H). C NMR (101 MHz, CD CN), d, ppm:
2
C H N O, Pna2 , a = 9.6713(4), b = 9.0619(4), c = 15.8838(7) Å, crystals of the binuclear complex with the same crystal struc-
1
7
16
2
1
3
V = 1392.06 Å , Z = 4, R = 0.030, CCDC 1538863.†
ture parameters.
1
ꢀ
1
1-Phenyl-3(phenylimino)indolinone-2-one (L9). IR (KBr) n, cm
:
2 2 2
[Cu (m-Br) (L3) ] (C4). The complex was prepared in a similar
1
737 (nCQO), 1653 (nCQN). MS (ESI), m/z (%): 299.119, 321.101. way (both methods worked) to C3. MW = 815.54. Calculated for
1
H NMR (CD CN), d, ppm: 7.73 (dd, J = 7.5, 0.7 Hz, 0.18H), 7.61 C H Br Cu N O – C (50,07), H (3,95), N (6,87); estimated – C
3
34 32
2
2 4 2
ꢀ1
(dd, J = 10.7, 4.5 Hz, 1.71H), 7.53–7.39 (m, 4.99H), 7.38–7.25 (m, (50.12), H (3,94), N (7,36). IR (KBr) n, cm : 1717 (nCQO). ESI
+
+
1
6
.97H), 7.23–7.12 (m, 0.33H), 7.09–6.98 (m, 1.97H), 6.79 (td, J = (MeOH), m/z: 591.1803 [M ꢀ 2Br] , 735.0265 [M ꢀ Br] .
13
.9, 3.2 Hz, 1.83H), 6.59 (dd, J = 7.9, 1.0 Hz, 0.82H). C NMR
CN), d, ppm: 163.3, 155.4, 151.9, 149.3, 135.1, 135.0, 134.9, 14.1074(5) Å, b = 94.972(3)1, V = 3142.24 Å , Z = 4, R
30.9, 129.6, 129.5, 129.4, 127.8, 127.6, 126.8, 126.2, 124.5, CCDC #1538881.†
34 2 2 4 2
C H32Br Cu N O , P2/c, a = 26.9791(11), b = 8.2871(3), c =
3
(CD
3
1
= 0.039,
1
196 | New J. Chem., 2019, 43, 188--198
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